JP7232484B2 - Hair treatment composition and hair treatment method - Google Patents

Description

The present invention relates to a hair treatment composition containing, as an active ingredient, a complex comprising a bifunctional compound, more preferably a bifunctional compound having 6 (C6) or more carbon atoms, and a thiol, and further the hair treatment. It relates to a hair treatment method using a composition for hair.

For the purpose of improving the condition of hair, many hair treatment compositions containing organic acids such as bifunctional compounds have been developed. For example, a perming agent containing thioglycolic acid, adipic acid, etc. (see Patent Document 1), a hair reducing substance having a thiol group, and a first hair shape control agent containing a bifunctional compound suitable for adipic acid. A hair treatment method comprising applying to hair a composition (see Patent Document 2), a first composition containing a bifunctional compound such as adipic acid or muconic acid, and a second composition having a different pH. Such compositions containing no reducing agent have been disclosed (see Patent Document 3).

WO 2006/011771 Patent No. 5112836 WO2018/191362

A composition for hair treatment with a long-lasting effect and safety for the purpose of improving hair quality during straightening, dyeing and bleaching, improving hair quality during wave perm and straight perm, and as shampoo and hair treatment. things were wanted. Patent Documents 1 and 2 disclose a first agent for perming agents containing a dicarboxylic acid. The problem to be solved by the present invention and the problems of these inventions are different. Further, Patent Document 3 discloses a composition containing no reducing agent in an embodiment, and the dicarboxylic acid alone acts on the hair.

The present invention has been achieved by the inventors through the finding that a complex consisting of a specific dicarboxylic acid and a thiol can provide a remarkable hair-improving effect. That is, the present invention relates to a hair treatment composition comprising a complex comprising a dicarboxylic acid and a thiol as an active ingredient, wherein the dicarboxylic acid is a dicarboxylic acid having 6 to 10 carbon atoms and a cosmetically acceptable One or more selected from the group consisting of salts thereof, and the thiols are one or more selected from the group consisting of aminothiols and cosmetically acceptable salts thereof. The complex may be a complex formed by reacting thiols/dicarboxylic acid at a molar ratio of 0.01-100. It may also be a complex obtained by reacting at a molar ratio of thiols/dicarboxylic acid=1 or more.

Another aspect of the present invention is a hair treatment composition containing a dicarboxylic acid and a thiol, wherein the dicarboxylic acid is a group consisting of a dicarboxylic acid having 6 to 10 carbon atoms and a cosmetically acceptable salt thereof. and the thiols are one or more selected from the group consisting of aminothiols and cosmetically acceptable salts thereof.

Furthermore, the present invention is a hair treatment composition that does not substantially contain active ingredients other than dicarboxylic acids, thiols, and complexes of dicarboxylic acids and thiols. Another present invention is a group consisting of a curly hair straightening agent, a hair quality improving agent for dyeing or bleaching, a hair quality improving agent for wave perm or straight perm, a shampoo, a hair treatment agent, and a hair styling agent (hair styling agent). Although it is one or more selected from, still another present invention is not the first agent or the second agent for wave perm or straight perm.

Thiols in the present invention are aminothiols, specifically cysteamine, cysteine, amidinocysteine, aminothiophenol, mercaptopyridine, homocysteine, aminoundecanethiol, and cosmetically acceptable salts thereof. It may be one or more selected from the group consisting of: The dicarboxylic acid in the present invention is selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, hexenedioic acid, heptenedioic acid, octenedioic acid, muconic acid, and cosmetically acceptable salts thereof. can be one or more.

The hair treatment composition of the present invention is obtained by a manufacturing method including at least a mixing step of mixing dicarboxylic acid and thiols at high temperature. Complexes formed by dicarboxylic acids and thiols are obtained by the mixing step. The mixing step can be a mixing step in which the dicarboxylic acid and the thiols are mixed at 60-100°C. Also, the mixing step can be a mixing step in which active ingredients other than dicarboxylic acids, thiols, their solvents, and pH adjusters are substantially absent.

Furthermore, the present invention is a hair treatment method, comprising: a step of applying the above hair treatment composition or a hair treatment composition produced by the above production method to the hair; and a heating step of heating the The heating step may be a step of heating the surface temperature of the hair to 40-60°C, 80°C, 100°C, 120°C, 140°C, 160°C, or 180°C.

In another hair treatment method of the present invention, the hair treatment composition is applied to the hair as the first or second agent for wave perm or straight perm, and the hair quality at the time of straightening, dyeing and bleaching is not affected. The purpose is one or more selected from the group consisting of improvement, hair quality improvement during wave perm and straight perm, and shampoo and hair treatment. The hair treatment method of the present invention can be a non-therapeutic method.

INDUSTRIAL APPLICABILITY The present invention can provide a hair treatment composition that is safe for users because it comprises dicarboxylic acids and thiols that have been used as cosmetic materials. The hair treatment method using the hair treatment composition of the present invention is capable of straightening curly hair, improving hair quality during dyeing and bleaching, improving hair quality during wave perm and straight perm, shampooing and hair treatment. The effect lasts even after multiple shampoo washes.

When the hair treatment composition of the present invention is used for straightening curly hair, the hair is not twisted and the finish is soft. Furthermore, even after the curly hair straightening treatment, the curly hair straightening effect on the hair and the strong and flexible state of the hair are maintained. When the hair treatment composition of the present invention is used for dyeing and bleaching, the hair can be made soft while maintaining high elasticity. In addition, damage to the hair during bleaching is reduced, and twisting of the hair is reduced. When the hair treatment composition of the present invention is used for a wave perm or a straight perm, the hair can be softly finished, and the effect of the perm on the hair and the strength and flexibility of the hair can be maintained. When the hair treatment composition of the present invention is used for shampooing or hair treatment, unintended waviness of the hair can be softened, the elasticity of the hair can be increased, and the hair can be finished softly. These effects can be maintained even after washing the hair multiple times with shampoo.

In particular, in the hair treatment method of the present invention, the effect can be obtained by heating the hair after applying the hair treatment composition to the hair. It is advantageous in that the effect can be obtained even in the step of This temperature range has a low risk of damaging the hair, and is the temperature range for routine hairdressing at home. Therefore, the composition and method of the present invention can provide hair treatment effects without using specialized equipment.

1 is a photograph showing the effect of improving the curl formation and durability of hair treated with the hair treatment composition of the present invention as an intermediate treatment agent for permanent waving agents. 4 is a photograph showing the straightening effect of the hair treatment composition of the present invention on curly hair of Ethiopian women. 1 is a photograph showing curl formation of bleached hair treated with the hair treatment composition of the present invention and effect of improving the durability thereof. 1 is a photograph showing curl formation of bleached hair treated with a shampoo agent containing the hair treatment composition of the present invention.

The present invention will be described in detail based on its embodiments, but the present invention is not limited by the embodiments.

The present invention is a hair treatment composition containing, as an active ingredient, a complex comprising a bifunctional compound, preferably a bifunctional compound having 6 (C6) or more carbon atoms, and a thiol. A bifunctional compound is a general term for compounds containing two functional groups, and specifically includes dicarboxylic acids, which are dicarbonyl compounds. In the hair treatment composition of the present invention, a complex comprising dicarboxylic acid and thiols contained in the composition acts on hair as an active ingredient. In the present invention, a complex refers to a state in which a plurality of molecules are associated or bound by intermolecular forces or covalent bonds, and includes compounds and associations composed of a plurality of molecules. In the hair treatment composition of the present invention, a complex formed by the reaction of thiols and dicarboxylic acid acts as an active ingredient.

Also, one embodiment of the present invention is a hair treatment composition containing a dicarboxylic acid and a thiol. A complex formed by dicarboxylic acid and thiols acts on hair as an active ingredient, but dicarboxylic acid and/or thiols alone may act on hair. Specifically, the present invention is a hair treatment composition containing a dicarboxylic acid and thiols, wherein the dicarboxylic acid is selected from muconic acid, adipic acid, octenedioic acid, and cosmetically acceptable salts thereof. It may be one or more selected from the group consisting of: The thiols are one or more selected from the group consisting of aminothiols and cosmetically acceptable salts thereof, and may be cysteamine or a cosmetically acceptable salt thereof.

The complex, which is the active ingredient of the present invention, is a complex that can be formed by reacting a dicarboxylic acid and a thiol in a solvent such as water or ethanol, preferably in an aqueous solution. Specifically, a thiol group possessed by a thiol and an alkene possessed by a dicarboxylic acid, or a double bond in an alkene formed by reduction of a dicarboxylic acid acted on a thiol-ene reaction to induce a complex, Examples thereof include complexes attracted by intermolecular hydrogen bonds formed between dicarboxylic acids and thiols. The complex can be obtained by a mixing step of mixing dicarboxylic acid and thiols at elevated temperature.

A dicarboxylic acid refers to a compound with two carboxy groups. Among dicarboxylic acids, α,ω-dicarboxylic acids are preferably used in the hair treatment composition of the present invention. A linear or branched alkane or alkene having 6 to 10 carbon atoms with carboxy groups added to both ends, more preferably a linear or branched alkane or alkene having 6 to 8 carbon atoms with carboxy groups at both ends is used.

The dicarboxylic acid used in the hair treatment composition of the present invention is preferably a linear saturated dicarboxylic acid and/or unsaturated dicarboxylic acid. Saturated dicarboxylic acids include hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, and unsaturated dicarboxylic acids include hexenedioic acid, heptenedioic acid, octenedioic acid, nonene diacid, decenedioic acid, hexadienedioic acid, heptadienedioic acid, octodienedioic acid, nonadienedioic acid, decadienedioic acid and the like.

Dicarboxylic acids used in the hair treatment compositions of the present invention include adipic acid, pimelic acid, suberic acid, azelaic acid, hexenedioic acid, heptenedioic acid, octenedioic acid, muconic acid, and cosmetically acceptable thereof. It may be one or more selected from salts, more preferably one or more selected from the group consisting of adipic acid, octenedioic acid, muconic acid, and cosmetically acceptable salts thereof. A high hair treatment effect was confirmed in the hair treatment compositions containing these complexes of dicarboxylic acids and thiols.

Any dicarboxylic acid having cis/trans isomers can be used as long as the effects of the present invention are achieved. For example, muconic acid has three cis/trans isomers: trans, trans type, cis, trans type, and cis, cis type. When muconic acid is used as a dicarboxylic acid, any isomer can be used in the present invention, but trans, trans-type muconic acid reacts with thiols in a shorter time than other isomers. It has the advantage that complex formation is possible.

Thiols refer to compounds having at least one thiol group. The thiol used in the hair treatment composition together with the dicarboxylic acid in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but it is specifically aminothiol. Aminothiols, also called mercaptoamines, are thiols with one or more amino groups.

The aminothiols used in the hair treatment compositions of the present invention are specifically selected from cysteamine, cysteine, amidinocysteine, aminothiophenol, mercaptopyridine, homocysteine, aminoundecanethiol, and cosmetically acceptable salts thereof. It may be one or more selected from the group consisting of: Among thiols, compounds having primary amines such as cysteamine and cysteine are preferably used, and cysteamine is more preferably used.

The pH of the hair treatment composition of the present invention is preferably weakly acidic to weakly alkaline, more preferably in the neutral range. Specifically, the pH is 5-8, more preferably 5.5-7.5, even more preferably 6-7. After the mixing step described below, the pH of the composition can be adjusted to the desired pH.

The hair composition of the present invention can also be blended into hair dyes, bleaching agents, and perming agents. In that case, the pH of the hair treatment composition of the present invention is preferably neutral to alkaline, more preferably neutral to weakly alkaline. Specifically, the pH is 7-12, more preferably 8-11.

The hair treatment composition of the present invention contains a complex formed by a dicarboxylic acid and a thiol as an active ingredient, but may or may not contain an active ingredient other than the dicarboxylic acid and the thiol or the complex. may This is because even if the composition does not contain active ingredients other than dicarboxylic acid, thiols, or a complex thereof, the composition containing at least the complex can provide effects on the hair. Here, active ingredients other than dicarboxylic acids, thiols, and their complexes refer to ingredients that give some effect to the hair when applied to the hair. Reducing agents, oxidizing agents such as sodium bromate and hydrogen peroxide, hyaluronic acid, chondroitin sulfate, collagen, glycerin, xylitol, glucose, sucrose, amino acids, derivatives thereof, salts thereof, etc., xanthan gum, guar gum, pectin and surfactants such as thickeners, anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Here, active ingredients other than dicarboxylic acids, thiols, and their complexes include antioxidants, preservatives, preservatives, fragrances, coloring agents, pH adjusters, etc., which are not intended to have a direct effect on the hair. No ingredients included.

Another embodiment of the present invention is a hair treatment composition obtainable by a method comprising at least a mixing step of mixing a dicarboxylic acid and a thiol at elevated temperature. This is because mixing at a high temperature promotes the formation of a complex of dicarboxylic acids and thiols, which are active ingredients.

In the mixing step, in addition to dicarboxylic acids and thiols, the presence of solvents (water, ethanol, etc.) that do not inhibit complex formation between dicarboxylic acids and thiols, and pH adjusters are allowed, but other active ingredients are allowed. It is preferred to mix the dicarboxylic acid and thiols in an environment substantially absent. This is because mixing in the presence of other components may inhibit the formation of complexes between dicarboxylic acids and thiols.

Specifically, the mixing step is a step of mixing dicarboxylic acids and thiols dissolved in a solvent (water, ethanol, etc.) in a high-temperature environment. It is desirable that the solvent (water, ethanol, etc.) does not substantially contain components that inhibit complex formation between the dicarboxylic acid and the thiols, except for acids or alkalis for adjusting the pH. The term "substantially absent" means that the ingredients are not intentionally contained in the manufacturing process of the hair treatment composition, and substances dissolved in the solvent (water, ethanol, etc.) from the beginning, The presence of substances dissolved in the solvent from the external atmosphere during the process is permissible.

In one embodiment of the present invention, the mixing step is a production method in which active ingredients other than dicarboxylic acids, thiols, their solvents (water, ethanol, etc.) and pH adjusters are substantially absent. . Active ingredients that are not allowed to exist here are those that can inhibit the formation of complexes between dicarboxylic acids and thiols, and the presence of ingredients that do not inhibit the formation of complexes between dicarboxylic acids and thiols is acceptable. .

In the mixing step, the temperature for mixing dicarboxylic acid and thiols is 40-120°C, preferably 60-100°C. The temperature is more preferably 80 to 100° C. When the solvent is water, it may be heated to boiling under normal pressure. The time of exposure to high temperature is not limited, but is specifically from 1 minute to 24 hours, preferably from 1 hour to 6 hours. The mixing step may also be carried out under high pressure, in which case the composite can be obtained at a lower temperature and for a shorter period of time as compared to the mixing step under atmospheric pressure.

In the mixing step, it is not essential to adjust the pH of the mixed solvent of dicarboxylic acid and thiols, but if the dissolution of dicarboxylic acid and / or thiols in the solvent is insufficient, by adjusting the pH, dissolution is promoted. Since dicarboxylic acid exhibits acidity, it may be mixed in the presence of a pH adjuster exhibiting alkalinity. The pH of the solvent during mixing is not limited, but it is preferably in the acidic to weakly alkaline range, more preferably in the acidic range. Specifically, the pH can be 4-9, 4-7, 4-6.

The amount (molar ratio) of dicarboxylic acid and thiol in the hair treatment composition of the present invention is not limited, and thiol/dicarboxylic acid = 0.01 to 100 (that is, the amount of thiol relative to the amount of dicarboxylic acid). The molar ratio of the amount of substances can be 0.01 to 100), but the molar ratio of thiols / dicarboxylic acid = 1 or more (that is, the molar ratio of the amount of thiols to the amount of dicarboxylic acid is 1 or more) Preferably. Specifically, thiols/dicarboxylic acid=1 to 100, 1 to 10, 1 to 5, or 1 to 3. This is because if the amount of the thiol substance is less than the amount of the dicarboxylic acid, the formation of the complex may be insufficient and the effect of improving hair quality may not be sufficiently exhibited.

The present invention provides a hair treatment method comprising at least an application step of applying a hair treatment composition to the hair, and a heating step of warming the hair after the application step. Another embodiment of the hair treatment method of the present invention comprises, following the application step, the hair comprising a washing step of rinsing the hair treatment composition from the hair, and a heating step of warming the hair rinsed with the hair treatment composition. processing method.

The heating temperature in the heating step is not limited as long as it is a temperature at which the effect of the hair treatment composition of the present invention can be obtained. ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, more preferably the surface temperature of the hair is 40 ~ 60 It is a step of heating to ℃.

The hair treatment method of the present invention is advantageous in that the effect can be obtained even when the surface temperature of the hair is 40 to 60°C. This temperature range has a low risk of damaging the hair and is a temperature range for heating in daily hairdressing at home. Therefore, according to the present invention, the hair treatment effect of the present invention can be obtained without using specialized equipment.

In another embodiment, the hair treatment method provided by the present invention is selected from the group consisting of straightening, improving hair quality during dyeing and bleaching, improving hair quality during wave perm and straight perm, and shampooing and hair treatment. for the purpose of one or more

One embodiment of the hair treatment composition of the present invention is a hair quality improving agent containing the hair treatment composition and used for the purpose of improving hair quality during perming. In another embodiment, the hair quality improving agent is used not as the first or second agent for wave perms or straight perms, but as an intermediate agent therefor. Specifically, the first agent is applied to the hair, and after the hair is sufficiently reduced, the hair treatment composition of the present invention is applied. Upon application, the hair treatment composition of the present invention may be applied alone, or the hair treatment composition of the present invention and the first agent may be mixed and applied. Leave the hair in the applied state, wash off the first agent and the hair treatment composition of the present invention, heat and dry the hair, if necessary further heat using a hair iron or the like, and apply the second agent. apply. As a result, the hair has a soft finish, and the state of strong and flexible hair is maintained even after repeated shampooing after permanent treatment.

In another embodiment, the present invention provides a hair straightener containing a hair treatment composition. When straightening curly hair, the straightening agent is applied to the hair alone or mixed with the first agent for straightening curly hair, left to stand, washed off, dried by heating the hair, and if necessary, using a curling iron or the like. and apply the second agent. As a result, the hair is free from twisting and has a soft finish, and even after repeated shampooing after straightening treatment, the hair remains strong and flexible.

In another embodiment, the present invention provides an agent for improving hair quality during dyeing or bleaching, containing the hair treatment composition. The hair quality improving agent is mixed with the first agent and the second agent containing the oxidation dye, or mixed with the mixed liquid of the first agent and the second agent, applied to the hair, left to stand, rinsed off, and applied to the hair. Dry it with heat, and if necessary, heat it further with a hair iron or the like. As a result, an unpleasant odor immediately after dyeing and bleaching is suppressed, and the hair can be finished with high elasticity and softness. In addition, damage to the hair during bleaching is reduced, and twisting of the hair is reduced. That is, the present invention can be a hair dye or bleach containing the hair treatment composition.

In yet another embodiment, the present invention provides shampoos and hair treatments containing the hair treatment composition. A shampoo agent or hair treatment agent alone or mixed with an existing shampoo agent or hair treatment agent is applied to the hair, left to stand, washed off, heated and dried, and if necessary, using a hair iron or the like. heat further. As a result, the hair can be finished with high elasticity and softness. After that, even if the hair is washed with shampoo, the elasticity and softness of the hair continue.

In another embodiment of the hair treatment composition of the present invention, the present invention provides a hair styling agent (hair styling agent) containing the hair treatment composition. The hairdressing agent of the present invention can maintain high elasticity and softness of the hair in a styled state, and can impart a high hairstyling effect.

In another embodiment of the hair treatment composition of the present invention, the present invention provides a hair tonic and/or hair restorer containing the hair treatment composition. The hair nourishing agent and/or hair restorer of the present invention can impart a high hair nourishing effect and/or hair growing effect by maintaining high elasticity and softness of the hair.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

1. Production of the hair treatment composition of the present invention

As Experimental Example 1, a hair treatment composition containing a complex of muconic acid and cysteamine was produced. Of the three isomers of muconic acid, trans and trans muconic acid were used. 1.42 g of muconic acid was added to 10 g of purified water, and after adding 3 g of aqueous ammonia for pH adjustment, the mixture was heated to 80°C. After confirming that muconic acid was dissolved, 0.77 g of cysteamine was added, heated to boiling (up to 100°C) while mixing, and maintained at the boiling state (100°C) for 3 minutes to obtain a complex consisting of muconic acid and cysteamine. got a body Stop heating, allow to stand until normal temperature, and after confirming that there is no undissolved residue, adjust the pH to around 7.0 with aqueous ammonia, add purified water, and the final concentration of muconic acid and cysteamine becomes 10% by mass. was prepared as follows.

As Experimental Example 2, a hair treatment composition containing a complex of adipic acid and cysteamine was produced. After adding 1.46 g of adipic acid to 10 g of purified water and adding 3 g of aqueous ammonia for pH adjustment, the mixture was heated to 80°C. After confirming that adipic acid was dissolved, 0.77 g of cysteamine was added, heated to boiling (up to 100°C) while mixing, and maintained at the boiling state (100°C) for 3 minutes to obtain a complex consisting of adipic acid and cysteamine. got a body Stop heating, allow to stand until normal temperature, and after confirming that there is no undissolved residue, adjust the pH to around 7.0 with ammonia water, add purified water, and the final concentration of adipic acid and cysteamine becomes 10% by mass. was prepared as follows.

As Experimental Example 3, a hair treatment composition was produced using muconic acid and thioglycerin. The production was carried out under the same conditions as in Experimental Example 1, except that 1.08 g of thioglycerin was added instead of cysteamine.

As Experimental Example 4, a hair treatment composition was produced using adipic acid and thioglycerin. The production was carried out under the same conditions as in Experimental Example 2, except that 1.08 g of thioglycerin was added instead of cysteamine.

As Experimental Example 5, a hair treatment composition was produced using muconic acid and glyceryl thioglycolate. Except for adding 1.66 g of glyceryl thioglycolate instead of cysteamine in Experimental Example 1, the production was carried out under the same conditions.

As Experimental Example 6, a hair treatment composition was produced using adipic acid and glyceryl thioglycolate. The production was carried out under the same conditions as in Experimental Example 2, except that 1.66 g of glyceryl thioglycolate was added instead of cysteamine.

As Experimental Example 7, a hair treatment composition was produced using adipic acid and ammonium thioglycolate. The production was carried out under the same conditions as in Experimental Example 2, except that 2.18 g of a 50% by weight aqueous ammonium thioglycolate solution was added instead of cysteamine.

Furthermore, as Comparative Example 1, a hair treatment composition was produced using fumaric acid and cysteamine. It was produced under the same conditions as in Experimental Example 2, except that 1.16 g of fumaric acid was added instead of adipic acid.

Furthermore, as Comparative Example 2, a hair treatment composition was produced using succinic acid and cysteamine. It was produced under the same conditions as in Experimental Example 2, except that 1.18 g of succinic acid was added instead of adipic acid.

2. Evaluation of the hair treatment composition of the present invention (1): Evaluation of wave-forming power during heat treatment and its durability

The hair treatment composition of the present invention was evaluated. Thirty to forty healthy human hairs (mean length 25 cm) were tufted and fixed in a zig-zag roll on a plastic measuring comb. According to the Kirby method (reference: Donald H. Kirby, Drug and Cosmetic Industry, 80 (3), 314-315, 397-400 (1957)), the hair was treated with a 10% by mass aqueous solution of ammonium thioglycolate in a perming agent No. 1. (pH 9.2) for 10 minutes and then rinsed with running water at 40°C for 30 seconds. Thereafter, the hair was immersed in each hair treatment composition of Experimental Example 1, Experimental Example 2, or Comparative Example 1 for 2 minutes, taken out, and dried with a towel.

The hair fixed to the comb for measurement was heated at 40°C, 60°C, or 80°C. Using a hair dryer, hot air was applied to the hair fixed to the comb for measurement for 3 minutes so that the surface temperature of the hair was 40°C, 60°C, or 80°C, and then left at room temperature of 15 to 20°C for 7 minutes. The hair was immersed in a second agent consisting of a 6% by mass sodium bromate aqueous solution for 10 minutes.

The waving power of each condition on hair was measured. The waving power is expressed as the distance between the peak of one wave and the peak of the adjacent wave formed on hair treated at each temperature. The shorter the distance, the stronger the waving force on the hair.

At the same time, the tactile sensation of the hair immediately after hair treatment was evaluated and scored. 0 is worse than before treatment, 1 is no change from before treatment, 2 is slightly improved compared to before treatment, 3 is clearly better than before treatment, A rating of 4 was given when the results were significantly better than before the treatment.

Furthermore, the durability of wave formation to shampoo washing was evaluated by the following method. The wavy hair is rubbed with an aqueous solution containing 2% by weight of shampoo containing sodium laureth sulfate as the main ingredient (hereinafter referred to as "aqueous shampoo solution"), rinsed with running water at 40°C for 30 seconds, and then towel-washed. The moisture on the hair was wiped off with , and the hair was dried by blowing hot air at 80°C with a hair dryer from a distance of 30 cm or more. This treatment was repeated, and it was verified whether the tactile sensation obtained immediately after wave formation changed or not, and the number of shampoo washings at which the wave formation power was lost was clarified. It was determined that the wave-forming ability was lost when the peak-to-peak distance of the wave was more than doubled immediately after formation.

For high durability to shampoo wash, the hair was treated with accelerated aging conditions. That is, the hair was immersed in an aqueous shampoo solution at 40°C for 2 hours, rinsed with running water at 40°C for 30 seconds, wiped off the moisture on the hair with a towel, and was blown with hot air at 80°C with a hair dryer from a distance of 30 cm or more. It was applied and dried. It was confirmed that this treatment had the same effect on the hair as the above shampoo washing 28 times. Therefore, by combining this accelerated aging treatment with the above-mentioned normal shampoo washing treatment, the number of shampoo washings at which the wave-forming power is lost was clarified.

Table 1 shows the evaluation results. In Experimental Example 1, Experimental Example 2, and Comparative Example 1, a good waving force of 20 mm or less was confirmed under any conditions. In Comparative Example 1, the effect persisted after 29 washings with a heating treatment at a hair surface temperature of 60°C and 57 washings with shampoo at a heating treatment with a hair surface temperature of 80°C. In Experimental Example 1, durability against shampoo washing was confirmed for 38 times or more with a heating treatment at a hair surface temperature of 60°C, and in Experimental Example 2 at a heating treatment at a hair surface temperature of 40°C for 38 times or more. That is, in Experimental Examples 1 and 2, the durability obtained in the heating treatment at a hair surface temperature of 40 to 60°C was the same as in Comparative Example 1 in the heating treatment at 40 to 60°C. It was higher than the durability and comparable to the persistence obtained by heating treatment at 80°C in the comparative example.

In addition, the tactile sensation immediately after wave formation was examined in the experimental example and the comparative example. Under all conditions, the texture of the hair was improved compared to before treatment. However, in Comparative Example 1, when the surface temperature of the hair was 60°C or less, the tactile sensation of the hair was not permanent, but was semi-permanently lost by washing with shampoo. Without it, the tactile sensation was not permanent. On the other hand, in Experimental Example 1, the hair surface temperature was 60°C, and in Experimental Example 2, the hair surface temperature was 40°C and 60°C. A tactile sensation was obtained. Therefore, it was found that in Experimental Examples 1 and 2, a remarkable hair treatment effect can be obtained with a lower temperature treatment than in Comparative Example 1.

3. Evaluation of the Hair Treatment Composition of the Present Invention (2): Evaluation of Wave Forming Power and Its Sustainability When Treated at Normal Temperature Further , the waving power and its durability were evaluated when the hair was treated at room temperature. The hair fixed to the measurement comb was immersed in each of the hair treatment compositions of Experimental Examples 1 to 7 or Comparative Examples 1 and 2 for 2 minutes in the same manner as in "2.". In the blank test, the hair was immersed in purified water for 2 minutes. The hair was taken out and the moisture on the hair was wiped off with a towel. The hair fixed to the measurement comb is left at 15 to 20 ° C for 10 minutes, immersed in the second agent consisting of 6 mass% sodium bromate aqueous solution for 10 minutes, and the measurement comb is removed from the hair taken out. Dried at ~20°C.

Evaluation results are shown in Tables 2 and 3. In Experimental Examples 1 to 6, good wave forming power of 20 mm or less was confirmed in the hair under any conditions, and the wave was maintained even after 5 to 10 shampoo washes. In Experimental Examples 3 and 4, the feel of the hair did not change from that before treatment, but in Experimental Examples 1 and 2, and Experimental Examples 5 and 6, improvement from that before treatment was observed. The tactile sensation of the hair obtained in each experimental example was semi-permanent.

4. Evaluation of the hair treatment composition of the present invention (3): Evaluation of curl-forming power and its durability 30 to 40 healthy human hairs (average length 25 cm) were treated with a 10% by mass aqueous solution of ammonium thioglycolate. 1st agent (pH 9.2) for 10 minutes and rinsed with running water at 40°C for 30 seconds. Thereafter, the hair was immersed in each hair treatment composition of Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, Experimental Example 5, Experimental Example 6 or Experimental Example 7 for 2 minutes. The blank test hair was immersed in purified water for 2 minutes. It was rinsed with running water at 40°C for 30 seconds, and excess water was wiped off with a towel. After winding the hair three times around a cylindrical curling iron with a diameter of 25 mm, after the surface temperature of the hair reaches 180°C, heat it with the curling iron for 2 minutes to form a curl, then remove it from the curling iron and leave it at room temperature for 7 minutes. I left it. After that, the hair was immersed for 10 minutes in the second part of a perming agent consisting of a 6% by mass sodium bromate aqueous solution, taken out, and then dried at room temperature.

The diameter or circumference of the curl formed on the hair was measured and evaluated as the curl forming force. A smaller measured value indicates a stronger curl-forming force on the hair. In addition, in the same manner as described above, the durability of curl formation against shampoo washing was investigated, and the tactile sensation of hair immediately after hair treatment was evaluated and scored.

Evaluation results are shown in Tables 4 and 5. In Experimental Example 3, no curl-forming ability was observed on the hair, but in Experimental Examples 1 and 2 and Experimental Examples 4-7, curl-forming ability was confirmed. In particular, the curl forming power of Experimental Examples 1 and 2 was maintained even after shampooing 85 times or more, respectively, and had high durability. Under any conditions, the tactile sensation immediately after curling was improved, but in Experimental Examples 1 and 2, the tactile sensation was particularly significantly improved.

The tactile feel of the hair obtained in Experimental Examples 1 and 2 was permanent, and the durability of the effect was remarkable even when compared with other Experimental Examples and Comparative Examples. The tactile sensation in Experimental Examples 1 and 2 did not deteriorate even after washing with shampoo 100 times or more.

Furthermore, each composition of Experimental Example 1, Experimental Example 2, Comparative Example 1 or Comparative Example 2, and purified water instead of Experimental Example or Comparative Example as a blank test, were applied to the hair immediately after treatment under the same conditions as described above. Figure 1A shows a photograph of the hair after 87 equivalent shampoo treatments, i.e., 3 accelerated aging treatments and 3 regular shampoos are shown in Fig. 1B. A heating rod with a diameter of 15 mm was used instead of a curling iron with a diameter of 25 mm to heat the hair.

As shown in FIG. 1A, Experimental Example 1 (indicated as “Real 1” in the figure), Experimental Example 2 (indicated as “Real 2” in the figure), Comparative Example 1 (indicated as “Ratio 1” in the figure) ), and in Comparative Example 2 (indicated as “ratio 2” in the figure), the curl-forming force on the hair immediately after treatment was higher than that in the blank test (indicated as “blank” in the figure). was significantly stronger. In Comparative Examples 1 and 2, the ends of the hair lose their manageability after shampooing 87 times. maintained the same quality.

5. Evaluation of the hair treatment composition of the present invention (4): Evaluation of curly hair straightening power and its durability 30 to 40 curly hairs (average length 25 cm) of Japanese women were It was immersed for 10 minutes in the first agent of perming agent (pH 9.2), which was an aqueous solution of ammonium glycolate, and rinsed with running water at 40°C for 30 seconds. Thereafter, the hair was immersed in the hair treatment composition of Experimental Example 1 or Experimental Example 2 for 2 minutes, rinsed with running water at 40°C for 30 seconds, and excess water was wiped off with a towel. Using a flat iron, the hair was straightened from the root to the tip for 1 minute while pulling the hair little by little so as to remove twists from the root. Further, the hair was ironed once at a uniform speed for 3 seconds from the root to the tip of the hair, heat was applied again from the root of the hair, and the hair was left at room temperature for 7 minutes. Thereafter, the hair was immersed for 10 minutes in the second part of a perming agent consisting of a 6% by mass aqueous solution of sodium bromate, taken out, and then dried at room temperature.

As a result, the hair treated in Examples 1 and 2 had a soft finish. In particular, in Experimental Example 2, both softness and toughness were achieved, and the surface of the hair was glossy. As a result of measuring the durability of the curly hair straightening power against washing with shampoo, both Experimental Examples 1 and 2 were confirmed to have a high durability of 85 times or more.

Furthermore, another curly hair straightening test result is shown in FIG. Ethiopian women's hair, which tends to be very frizzy, was immersed in a 10% by mass aqueous solution of ammonium thioglycolate as the first agent for perming (pH 9.2) for 30 minutes, and then rinsed with running water at 40°C for 30 seconds. After that, the hair was immersed in each hair treatment composition of Experimental Example 1, Experimental Example 2, or Comparative Example 2 for 3 minutes. As a blank test, purified water was used in place of the experimental examples and comparative examples, and hair was treated under the same conditions. The hair was rinsed with running water at 40°C for 30 seconds, and excess water was wiped off with a towel. I removed more moisture with a low temperature dryer and slowly stretched my hair with an iron at 180°C.

Fig. 2A is a photograph of curly hair (20-30 strands, average length 15 cm) of an Ethiopian woman before treatment, and Fig. 2B is a photograph of the hair after treatment. Comparative Example 2 (indicated as “Comparison 2” in the figure) had the same condition as the hair used in the blank test (indicated as “Blank” in the figure), but the hair in Experimental Example 1 (“Example 1” in the figure) was used. ”) and Experimental Example 2 (shown as “Example 2” in the figure), the curly hair grew straight. Especially in Experimental Example 1, the ends of the hair were well organized, and an ideal curly hair straightening effect was confirmed.

6. Evaluation of the hair treatment composition of the present invention (5): Evaluation as a hair treatment agent for hair at each treatment temperature The hair treatment effects of the compositions of Experimental Examples 1 and 2 on healthy human hair or bleached hair were verified. . 30 to 40 normal human hair or bleached hair (average length 25 cm) are bundled, and the composition of Experimental Example 1, Experimental Example 2 or Comparative Example 2 is added to the composition so that the concentration of dicarboxylic acid and thiols is 0.5 mass. % and immersed in a liquid (pH 7) for 3 minutes and wiped off excess water. The hair was treated with a surface temperature of 20°C, 60°C, 80°C, or 120°C.

For the 20°C treatment, the hair is tightly wrapped around a 15 mm heat rod, left at 20°C (room temperature) for 10 minutes, any excess moisture is wiped off with a towel, and the hair is left for another minute. was removed from the heat rod. In the treatment to heat the hair to 60°C or 80°C, the hair is tightly wrapped around a 15 mm heat rod, heated for 10 minutes so that the surface of the hair reaches 60°C or 80°C, and left for another 1 minute before the heat rod is removed. After cooling, the hair was removed from the heat rod. In the treatment of heating the hair to 120°C, the hair is wrapped 3 times around a cylindrical curling iron with a diameter of 25 mm, heated to about 180°C for 10 minutes to form curls, then removed from the curling iron and left at room temperature. and left for 1 minute.

Each hair was immersed in an aqueous shampoo solution at 40°C for 10 seconds, rinsed with running water at 40°C for 10 seconds, and then wiped dry with a towel. The effect on hair was evaluated in terms of overall findings including percent curl formation, persistence of curl formation, and feel. The curl formation rate is the distance (curl diameter) from the point at which the root of the hair bundle begins to bend when the curl is formed, to the tip of the hair with the second longest tip in the hair bundle. Further, the distance from the starting point to the tip of the hair was measured with the hair bundle stretched out (hair length), and the curl formation rate was calculated as (hair length - curl diameter)/hair length x 100.

To evaluate the durability of curl formation, soak hair bundles in an aqueous shampoo solution, rinse with water, wipe off excess water with a towel, and leave to dry at room temperature once. The number of times of treatment until the hair tresses no longer rotate (the hair tresses do not rotate once) was measured. Furthermore, under the condition that the bleached hair was set at 80°C, evaluation was made using the above-mentioned tactile sensation score.

Table 6 shows the evaluation results using healthy hair, and Table 7 shows the evaluation results using bleached hair. In Experimental Examples 1 and 2, the curl formation rate was measured to be higher than that of Comparative Example in the treatment with the hair surface temperature of 40 to 180°C. In addition, in Experimental Examples 1 and 2, it was confirmed that curl formation persisted after shampooing at least twice by treating the surface temperature of the hair at 20 to 80°C. Curl formation was lost after one shampoo wash even under the temperature condition of . Also, Experimental Examples 1 and 2 improved the feel of bleached hair. As described above, the effect of the hair treatment agent containing the composition of the present invention was clarified.

Among the conditions described in Table 7, FIG. 3A shows a photograph of bleached hair immediately after treatment at 60° C., and FIG. 3B shows a photograph of bleached hair shampooed after treatment. Experimental Example 1 (indicated as “Ext. 1” in the figure), Experimental Example 2 (indicated as “Ext. 2” in the figure), and Comparative Example 2 (indicated as “Ratio 2” in the figure). ), and Comparative Example 1 (shown as “Ratio 1” in the figure) was used for the treatment. Purified water was used in the blank test (shown as "blank" in the figure) instead of the experimental examples and comparative examples. The bleached hair in the blank test was damaged by bleaching. The bleached hair treated in Experimental Examples 1 and 2 was soft and strong, and the curl was maintained even after shampooing. On the other hand, in Comparative Examples 1 and 2, the curls on the bleached hair disappeared by shampooing.

7. Evaluation of the hair treatment composition of the present invention (6): Evaluation of the composition obtained in the mixing step under each temperature condition as a hair treatment agent

Compositions obtained in the step of mixing dicarboxylic acids and thiols at 20°C (normal temperature), 60°C, or 80°C (Experimental Examples 8-14) and compositions obtained in the step of mixing at 100°C The effects of products (Experimental Examples 1 and 2) as hair treatment agents were verified.

In Examples 8-11, muconic acid and cysteamine were used to prepare hair treatment compositions. 1.42 g of muconic acid was added to 10 g of purified water and 0.77 g of cysteamine was added. Experimental Examples 8 and 9 were heated to 20°C (normal temperature), Experimental Example 10 was heated to 60°C, and Experimental Example 11 was heated to 80°C. When muconic acid and cysteamine were completely dissolved in water, heating was stopped in Experimental Examples 10 and 11, and the mixture was allowed to stand until the temperature returned to room temperature. Purified water and, if necessary, aqueous ammonia were added to adjust the pH to around 7, and purified water was added to adjust the final concentration of muconic acid and cysteamine to 10% by weight. Since it was difficult to adjust the pH to 7 under the condition of stirring at 20°C, Experimental Example 8 was adjusted to pH 6.5, and Experimental Example 9 was adjusted to pH 8.

In Examples 12-14, hair treatment compositions were prepared using adipic acid and cysteamine. 1.46 g of adipic acid was added to 10 g of purified water and 0.77 g of cysteamine was added. Experimental Example 12 was heated to 20°C (normal temperature), Experimental Example 13 was heated to 60°C, and Experimental Example 14 was heated to 80°C. When adipic acid and cysteamine were completely dissolved in water, heating was stopped in Experimental Examples 13 and 14, and the mixture was allowed to stand until the temperature returned to room temperature. The pH was adjusted to around 7.0 with aqueous ammonia, and purified water was added to adjust the final concentration of adipic acid and cysteamine to 10% by mass.

In addition to Experimental Examples 8 to 14, Experimental Example 1 containing a complex obtained by mixing muconic acid and cysteamine at 100°C, and a complex obtained by mixing adipic acid and cysteamine at 100°C. The effect of the composition of Experimental Example 2 containing hair treatment on healthy human hair or bleached hair was verified. A liquid obtained by diluting the composition of each experimental example so that the concentration of dicarboxylic acid and thiols was 0.5% by mass was used. Healthy hair and bleached hair were used, and the hair was heated to a surface temperature of 80°C. evaluated by the same method. Table 8 shows the evaluation results using healthy hair, and Table 9 shows the evaluation results using bleached hair. The compositions using muconic acid (Experimental Examples 8 to 11 and 1) gave excellent hair feel when the experimental examples obtained by mixing at 60°C or higher were used. In Examples 12-14 and 2), the curl retention and hair feel were excellent when the experimental examples obtained with mixing at 60° C. or higher were used. As described above, the higher the temperature of the mixing step, the better the curl durability and tactile score. It was suggested that

8. Evaluation of the hair treatment composition of the present invention (7)

The waving power and its persistence, and the curling power and its persistence of Experimental Examples 2 and 12 were evaluated. The evaluation method is the same as the method described above, and the wave forming power and its durability are evaluated by heating at a hair surface temperature of 40°C, and the curl forming power and its durability are evaluated at a hair surface temperature of 180°C. Each was compared by heating.

Table 10 shows the results. In Experimental Example 2, the tactile sensation during wave formation and curl formation was good, and persistence was observed even after washing with shampoo several times. On the other hand, in Experimental Example 12, compared with Experimental Example 2, the tactile sensation during wave formation and curl formation was inferior, and the durability after washing with shampoo was low.

9. Evaluation of the hair treatment composition of the present invention (8): Evaluation as the first agent for perming in digital perm (perm using a heat rod)

As Experimental Example 15, adipic acid and cysteamine were mixed at 40°C to produce a hair composition. 1.46 g of adipic acid was added to 10 g of purified water, 0.77 g of cysteamine was added, mixed at 40° C. and allowed to cool to room temperature when completely dissolved. The pH was adjusted to around 6.5 with aqueous ammonia, and purified water was added to adjust the final concentration of adipic acid and cysteamine to 10% by mass. In addition to the composition of Experimental Example 15, Experimental Example 12 was mixed at 20°C (normal temperature), Experimental Example 13 was mixed at 60°C, Experimental Example 14 was mixed at 80°C, and the composition of Experimental Example 2 was mixed at 100°C. The effect of the first agent for perming containing

The composition of each experimental example was diluted with an aqueous solution containing 10% by mass of ammonium thioglycolate so that the concentration of adipic acid and cysteamine was 0.5% by mass, and the pH was adjusted to 9, and these were permed. It was used as the first agent. 30 to 40 healthy human hairs (average length 25 cm) are immersed in each No. 1 agent for 10 minutes, rinsed with running water at 40°C for 20 seconds, and wrapped 4 times around a hot rod heated to 60°C. , and left for 10 minutes with felt wrapped around to prevent drying. After that, the hair was immersed in a 6% by mass aqueous solution of sodium bromate as the second part of the perming agent for 10 minutes, removed from the heat rod, and dried at room temperature.

Table 11 shows the evaluation results. In Experimental Examples 12 and 15, slight damage to the cuticle on the surface of the hair was confirmed, but in Experimental Examples 13, 14 and 2, there was no damage and the feel was good. I could see the sheen on my hair. In addition, the hair treated in Experimental Examples 13, 14 and 2 had a curling force of less than 30 mm in diameter, and each of them was confirmed to be durable after shampooing 33 times or more. As described above, the hair treatment compositions of Experimental Examples 13, 14 and 2 containing the complex obtained by mixing adipic acid and cysteamine at 60 to 100°C were mixed at 20 to 40°C. and 15, when used as the first agent for perm agents, a remarkable hair quality improving effect on hair was confirmed.

10. Evaluation of the hair treatment composition of the present invention (9): Evaluation of a shampoo agent containing the hair treatment composition of the present invention

The effects of shampoos containing the hair treatment compositions of Experimental Examples were verified. 6% by weight of lauroylmethylalanine TEA, 3% by weight of lauryl betaine, 1% by weight of cocamide methyl MEA, 1% by weight of cocamide DEA, and 0.3% by weight of polyquaternium-10; A stock solution of shampoo agent containing 1% by weight was prepared. For the blank test, instead of the experimental example, a shampoo stock solution containing purified water was used.

To warm water of about 40° C., about 10% by weight of the hot water was added to each of the shampoo stock solutions, and the mixture was stirred until it foamed. A bundle of 30 to 40 bleached human hairs (average length: 25 cm) was soaked in the shampoo liquid, taken out after 10 seconds, and the hair bundle was massaged by hand for about 10 seconds, then washed with running water at about 40°C. for about 10 seconds. The hair was wiped dry with a towel and dried with a cold hair dryer.

The hair was wound three times around a cylindrical curling iron with a diameter of 25 mm, and after the surface temperature of the hair reached 180°C, the hair was heated for 2 minutes to form a curl. Further, the curled hair was rinsed with running water of about 40°C for about 10 seconds, and the moisture on the hair was wiped off with a towel. It was set as the curl formation rate of the first time. Furthermore, each hair was additionally subjected to the same shampoo treatment twice using the same shampoo agent, and the curl formation rate of the second and third shampooing was measured.

Table 12 shows the results. Remarkable curls were formed on the hair using the shampoo containing Experimental Example 1 or Experimental Example 2. With the shampoo containing Experimental Example 1 or Experimental Example 2, the curls formed on the hair became stronger as the number of times of shampooing increased. On the other hand, almost no curls were formed when using a shampoo in which purified water was used in the experimental example.

Moreover, the hair using the shampoo containing Experimental Example 1 or Experimental Example 2 was lustrous and soft. These hairs had a particularly good feel to the touch after being heated with a hair iron, and the hair was not damaged by bleaching.

Furthermore, another verification result of the effects of shampoos containing experimental examples of the present invention is shown. By the same method as described above, in addition to the shampoo stock solution containing Experimental Example 1 or Experimental Example 2, a shampoo stock solution containing Comparative Example 1 was prepared. As a blank test, a shampoo stock solution containing purified water was used in place of the experimental examples and comparative examples. To warm water of about 40° C., about 10% by weight of the warm water was added to the hair, and the resulting mixture was stirred until foaming to obtain a shampoo. A bundle of 30 to 40 bleached human hairs (average length 25 cm) was immersed in a shampoo solution, taken out after 10 seconds, and rinsed with running water at about 40°C for about 10 seconds.

The hair was wound around a hair curler with a diameter of 25 mm and heated with a hair dryer for 3 minutes so that the surface of the hair was about 60°C. The hair was carefully removed from the hair curlers, gently rinsed with a hot shower at about 40°C, dried with a towel, and left to stand.

Table 13 shows the curl formation rate of the hair, and FIG. 4 shows a photograph of the state of the hair. The hair using the shampoo containing Experimental Example 1 (indicated as "Example 1" in the figure) and the shampoo containing Experimental Example 2 (indicated as "Example 2" in the figure) was subjected to a blank test. (indicated as "blank" in the figure) and hair using the shampoo containing Comparative Example 1 (indicated as "ratio 1" in the figure), the curl formation rate is extremely high, Curls were maintained even after hot shower.

11. Evaluation of hair treatment composition of the present invention (10): Verification of combination of dicarboxylic acid and thiols

Example 11, containing a conjugate of muconic acid and cysteamine, and Example 14, containing a conjugate of adipic acid and cysteamine, were used. Furthermore, Experimental Example 16 containing a complex consisting of (E)-Oct-4-ene-1,8-dioic acid, a type of octenedioic acid, and cysteamine was produced. It was produced under the same conditions as in Experimental Example 11 except that 1.73 g of (E)-Oct-4-ene-1,8-dioic acid was added instead of muconic acid.

Furthermore, Experimental Example 17 was produced using muconic acid and thiolactic acid, and Experimental Example 18 was produced using muconic acid and thiomalic acid. Experimental Example 17 was produced under the same conditions as in Experimental Example 11 except that 1.06 g of thiolactic acid was added instead of cysteamine. Experimental Example 18 was produced under the same conditions as in Experimental Example 11 except that 1.50 g of thiomalic acid was added instead of cysteamine.

Using the compositions of Experimental Examples 11, 14, and 16, the effect of hair treatment on normal human hair or bleached hair was verified. A bundle of 30 to 40 healthy human hairs or bleached hair (average length 25 cm) is diluted with the composition of the experimental example so that the concentration of dicarboxylic acids and thiols is 0.5% by mass (pH 7). ) for 3 minutes and wiped off excess water. The hair was tightly wrapped around a 15 mm heat rod, heated for 10 minutes so that the surface of the hair reached 80.degree.

Each hair was immersed in an aqueous shampoo solution at 40°C for 10 seconds, rinsed with running water at 40°C for 10 seconds, and then wiped dry with a towel. The effect on hair was evaluated in terms of overall findings including percent curl formation, persistence of curl formation, and feel. The curl formation rate is the distance (curl diameter) from the point at which the root of the hair bundle begins to bend when the curl is formed, to the tip of the hair with the second longest tip in the hair bundle. Further, the distance from the starting point to the tip of the hair was measured with the hair bundle stretched out (hair length), and the curl formation rate was calculated as (hair length-curl diameter)/hair length×100.

To evaluate the durability of curl formation, soak hair bundles in an aqueous shampoo solution, rinse with water, wipe off excess water with a towel, and leave to dry at room temperature once. The number of times of treatment until the hair tresses no longer rotate (the hair tresses do not rotate once) was measured.

Table 14 shows the evaluation results using healthy hair, and Table 15 shows the evaluation results using bleached hair. In Experimental Examples 11, 14, and 16, the condition of the hair was good, and highly persistent curls were formed on the hair.

Also, using Experimental Examples 11, 17 and 18 and a blank test (purified water), evaluation as a hair treatment agent was performed in the same manner as above. The results are shown in Table 16. In Experimental Example 11, as compared with Experimental Examples 17 and 18, remarkable effects were observed.

Furthermore, Experimental Example 11 using muconic acid, Experimental Example 14 using adipic acid, and Experimental Example 16 using (E)-Oct-4-ene-1,8-dioic acid, and fumaric acid were used. Using Comparative Example 1 and the same method as in "10.", the effects on human bleached hair were compared. A shampoo stock solution containing each composition of Experimental Example 11, Experimental Example 14, Experimental Example 16, or Comparative Example 1 was prepared, and a shampoo stock solution containing purified water was used as a blank test instead of Experimental Examples and Comparative Examples. board. To warm water of about 40° C., about 10% by weight of the warm water was added to the hair, and the resulting mixture was stirred until foaming to obtain a shampoo. A bundle of 30 to 40 bleached human hairs (average length 25 cm) was immersed in a shampoo solution, taken out after 10 seconds, and rinsed with running water at about 40°C for about 10 seconds.

The hair was wound around a hair curler with a diameter of 25 mm and heated with a hair dryer for 3 minutes so that the surface of the hair was about 60°C. The hair was carefully removed from the hair curlers, gently rinsed with a hot shower at about 40°C, dried with a towel, left to stand, and the curl formation rate was measured. The results are shown in Table 17. When the compositions of Experimental Examples 11, 14, and 16 were used, significantly higher curl formation rates than Comparative Example 1 were obtained.

12. Evaluation of the hair treatment composition of the present invention (11): Effect of pH in the mixing step on the hair treatment effect of the composition

As Experimental Example 19, a hair treatment composition was produced using muconic acid and cysteamine. Of the three isomers of muconic acid, trans and trans muconic acid were used. 1.42 g of muconic acid was added to 10 g of purified water and aqueous ammonia was added to bring the pH to 4.2. Furthermore, after heating to 80°C and confirming that muconic acid has dissolved, add 0.77 g of cysteamine, heat to boiling (up to 100°C) while mixing, and maintain the boiling state (100°C) for 3 minutes. A complex was obtained. Stop heating, allow to stand until normal temperature, and after confirming that there is no undissolved residue, adjust the pH to around 7.0 with aqueous ammonia, add purified water, and the final concentration of muconic acid and cysteamine becomes 10% by mass. was prepared as follows.

As Experimental Example 20, a hair treatment composition containing muconic acid and cysteamine was produced. Of the three isomers of muconic acid, trans and trans muconic acid were used. 1.42 g of muconic acid was added to 10 g of purified water, and aqueous ammonia was added to adjust the pH to 9.0. Further, after heating to 80°C and confirming that muconic acid had dissolved, 0.77 g of cysteamine was added, heated to boiling (up to 100°C) while mixing, and maintained in a boiling state (100°C) for 3 minutes. Stop heating, allow to stand until normal temperature, and after confirming that there is no undissolved residue, adjust the pH to around 7.0 with aqueous ammonia, add purified water, and the final concentration of muconic acid and cysteamine becomes 10% by mass. was prepared as follows.

Using the compositions of Experimental Examples 19 and 20, the effect of hair treatment on healthy human hair was verified. 30 to 40 healthy human hairs or bleached hairs (average length 25 cm) are bundled together, and the compositions of Experimental Examples and Comparative Examples are diluted so that the concentration of dicarboxylic acids and thiols is 0.5% by mass. (pH 7) for 3 minutes and wiped off excess moisture. The hair was tightly wrapped around a 15 mm heat rod, heated for 10 minutes so that the surface of the hair reached 60°C, left for another 1 minute to cool the heat rod, and then removed from the heat rod. The hair was immersed in an aqueous shampoo solution at 40°C for 10 seconds, rinsed with running water at 40°C for 10 seconds, and then wiped off with a towel to calculate the curl formation rate. Table 18 shows the evaluation results. Comparing the effects of Experimental Example 19 and Experimental Example 20, Experimental Example 19 was more durable in curling. Therefore, it was shown that the complex obtained by mixing in the acidic region exhibits a higher hair treatment effect.

13. Evaluation of hair treatment compositions of the present invention (12)

As Experimental Example 21, a hair treatment composition was prepared by mixing cysteamine and muconic acid at a molar ratio of 2:1. Of the three isomers of muconic acid, trans and trans muconic acid were used. 1.42 g of muconic acid was added to 10 g of purified water and dissolved by adding aqueous ammonia. After heating to 80°C and confirming that muconic acid has dissolved, add 2.27 g of cysteamine hydrochloride, heat to boiling (up to 100°C) while mixing, and maintain the boiling state (100°C) for 1 hour. , muconic acid and cysteamine were reacted. Stop heating, allow to stand until normal temperature, and after confirming that there is no undissolved residue, adjust the pH to around 7.0 with aqueous ammonia, add purified water, and the final concentration of muconic acid and cysteamine becomes 10% by mass. was prepared as follows.

Experimental Example 22 was produced under the same conditions as in Experimental Example 21, except that the reaction time between muconic acid and cysteamine was 6 hours. Experimental Example 23 was produced under the same conditions as in Experimental Example 21, except that cis, cis-type muconic acid was used instead of trans, trans-type muconic acid. Experimental Example 24 was produced under the same conditions as in Experimental Example 22, except that cis, cis-type muconic acid was used instead of trans, trans-type muconic acid.

Experimental Example 25 is a hair treatment composition obtained by mixing cysteamine and muconic acid at a molar ratio of 3:1. Other than that, it was manufactured under the same conditions as in Experimental Example 24. Experimental Example 26 is a hair treatment composition obtained by mixing cysteamine and muconic acid at a molar ratio of 1:1. Other than that, it was manufactured under the same conditions as in Experimental Example 24. Experimental Example 27 is a hair treatment composition obtained by mixing cysteamine and muconic acid at a molar ratio of 1:2. Other than that, it was manufactured under the same conditions as in Experimental Example 24.

Using the compositions of Experimental Examples 21 to 27, the hair treatment effect on healthy human hair was verified in the same manner as in "12.". Table 19 shows the production conditions and curl formation rate of each experimental example. A good hair treatment effect was obtained in the experimental examples using any of the isomers of muconic acid. was shown to be obtained. In addition, when cysteamine:muconic acid were mixed in a molar ratio of 1:1 to 3:1, a highly effective complex was obtained. However, when Example 25 mixed in a 3:1 molar ratio was used, a malodorous odor derived from thiols remained on the hair, and the feel of the hair treated with Example 25 was significantly lower than that of Example 24 or Example 26. , was somewhat bad.

Claims (14)

A hair treatment composition containing, as an active ingredient, a complex comprising a dicarboxylic acid and a thiol,
the dicarboxylic acid is one or more selected from the group consisting of muconic acid, adipic acid, octenedioic acid and cosmetically acceptable salts thereof;
The thiols are one or more selected from the group consisting of cysteamine, cysteine, amidinocysteine, homocysteine, and cosmetically acceptable salts thereof,
The complex is obtained by a mixing step of mixing the dicarboxylic acid and the thiols at 40-100°C ,
Composition for hair treatment. A hair treatment composition according to claim 1 , wherein the dicarboxylic acid is muconic acid or a cosmetically acceptable salt thereof. 3. A hair treatment composition according to claim 1 or 2 , wherein said thiol is cysteamine or a cosmetically acceptable salt thereof. The hair treatment composition according to any one of claims 1 to 3 , wherein the dicarboxylic acid and the thiols are reacted at a molar ratio of thiols/dicarboxylic acid = 0.01 to 100 to obtain the complex. A method of making things. 5. The method for producing a hair treatment composition according to claim 4 , wherein the molar ratio is thiols/dicarboxylic acid=1 or more. 6. The method for producing a hair treatment composition according to claim 4 or 5 , wherein the complex is obtained by a mixing step of mixing the dicarboxylic acid and the thiol at 40-100°C . The hair treatment product according to any one of claims 4 to 6, wherein the mixing step is performed in an environment that does not intentionally contain active ingredients other than the dicarboxylic acid, the thiols, their solvents, and the pH adjuster. A method of making the composition. Curly hair straightening agent, hair quality improving agent for dyeing or bleaching, hair quality improving agent for wave perm or straight perm, shampoo containing the hair treatment composition according to any one of claims 1 to 3. , hair treatment agents, and/or hair styling agents. 9. The hair quality improving agent for wave perms or straight perms according to claim 8 , which is not the first or second agent for wave perms or straight perms. an application step of applying the hair treatment composition according to any one of claims 1 to 3 or the hair treatment composition obtained by the production method according to any one of claims 4 to 7 to the hair;
and a heating step of heating the hair after the applying step. The heating step is a step of heating the hair so that the surface temperature is 40 to 180 ° C.
The hair treatment method according to claim 10 . The heating step is a step of heating the hair so that the surface temperature is 40 to 60 ° C.
The hair treatment method according to claim 10 . The hair treatment method according to any one of claims 10 to 12 , excluding a method of applying the hair treatment composition to the hair as a first or second agent for wave perms or straight perms. The hair treatment method aims at one or more selected from the group consisting of hair straightening, hair quality improvement during dyeing and bleaching, hair quality improvement during wave perm and straight perm, shampoo, and hair treatment. Item 1. The method for treating hair according to any one of items 10 to 13 .

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